ARTICLE IN PRESS

International Biodeterioration & Biodegradation 55 (2005) 279284 www.elsevier.com/locate/ibiod

Removal of organic pollutants and analysis of MLSSCOD removal relationship at different HRTs in a submerged membrane bioreactor
Nanqi Rena, Zhaobo Chena,, Aijie Wanga, Dongxue Hub
a

School of Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin 150090, China b School of Mathematics and Computer Science, Harbin Normal University, Harbin 150080, China

Abstract In order to investigate the inuence of hydraulic retention time (HRT) on organic pollutant removal in a submerged membrane bioreactor (SMBR), a laboratory-scale experiment was conducted using domestic sewage as inuent. The dissolved oxygen (DO) concentration was controlled at 2.03:0 mg L1 during the experimental period. The experiments demonstrated that when HRT was 3, 2 and 1 h, the reduction of chemical oxygen demand (COD) was 89.397.2, 88.597.3 and 8091.1%, and the efuent COD was 38.911.2, 41.610.8 and 63.435:8 mg L1 , respectively. It is suggested that an HRT of 1 h could meet the normal standard of discharged domestic sewage, and an HRT of 2 h could meet that of water reclamation. In addition, we use mathematical software MATLAB to analyse the relation of mixed liquor suspended solids (MLSS) and COD removal. The results showed that the optimum MLSS concentration should be maintained at around 6000 mg L1 in the SMBR. The results also showed that the COD removal was related to HRT t, inuent concentration S 0 and sludge loading rate for COD removal (N S ). Moreover, the high COD removal could be achieved through adjusting t, S0 and N S . r 2005 Elsevier Ltd. All rights reserved.
Keywords: Submerged membrane bioreactor (SMBR); Domestic sewage; HRT; MLSS; COD removal

1. Introduction It is well known that submerged membrane bioreactors (SMBRs) have the following advantages for wastewater treatment: high sludge concentration (Halil Hasara et al., 2002), high quality of efuent, long contact time between activated sludge and organic pollutants (Brindle and Stephenson, 1996), and complete separation of the hydraulic retention time (HRT) and sludge retention time (SRT) (Ueda et al., 1996; Devies et al., 1998; Guender and Krauth, 1998). Moreover, highly treated water in an SMBR is free from bacteria and has potential for municipal and industrial reuse (Xing et al., 1998). Although there are shortcomings of high-cost and high-energy consumption, SMBR technology has been applied to wastewater treatment and
Corresponding author. Fax: +86 451 8628 2009.

E-mail address: czbhdx@163.com (Z. Chen). 0964-8305/$ - see front matter r 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.ibiod.2005.03.003

reclamation previously (Chiemchaisri et al., 1993; Knoblock et al., 1994; Trouve et al., 1994). In Europe, America and Japan, SMBRs are used to rebuild sewage treatment plants and to reclaim wastewater. It is accepted that HRT is the key to further improving the capacity of an SMBR. At present, when an SMBR is used for domestic sewage treatment, the HRT is set at 1.57.5 h in laboratory-scale tests and at 2.734.2 h in the pilot-scale tests (Makoto et al., 1998; Urbain et al., 1998; Defrance and Jaffrin, 1999; Huang et al., 2000; Gu and He, 2002; Shim et al., 2002). When Rosenberger et al. (2002) used a membrane bioreactor to treat municipal wastewater at HRTs varying from 10.4 and 15.6 h, the concentration of mixed liquor suspended solids (MLSS) gradually increased and the chemical oxygen demand (COD) was reduced by 95%. Until now, the lowest HRT, 1.5 h, has been designed by Stefan and Walter (2001) to treat synthetic wastewater. The organic loading rate (OLR) in their study was in the

ARTICLE IN PRESS
280 N. Ren et al. / International Biodeterioration & Biodegradation 55 (2005) 279284

range 6.013:0 kg m3 day1 , and COD reduction was 495%. However, little has been reported on the optimum HRT needed to meet reused water quality standard, and how to control the operational conditions of SMBRs in order to reach different water quality standards. The purpose of this study was to investigate the shortest HRT needed in SMBRs in order to reach different water quality standards and the effect of HRT on COD removal. A laboratory-scale experiment was conducted using articial domestic sewage as inuent in an SMBR. The dissolved oxygen (DO) concentration was controlled at 2.03:0 mg L1 for the duration of the experimental period, and the HRT at 3, 2 and 1 h. The effect of MLSS on COD removal at different HRTs is examined.

bre membrane module. Aeration was employed to maintain an aerobic environment for the normal growth of activated sludge. The amount of air was adjusted using a gas ow meter and controlled at 0.30:5 m3 h1 . The water level in the SMBR was controlled by a ballcock in the water balance tank, which balanced the ux of efuent and inuent. 2.2. Substrate The articial domestic sewage containing mg L1 glucose (300400), beef grease (2040), peptone (2040), NH4 Cl (510), Na2 HPO4 (510) and NaH2 PO4 (510) was used as inuent. The inuent was maintained at pH 7.0 by adding NaOH. Inuent COD concentration was 350500 mg L1 . 2.3. Inoculation and acclimation of activated sludge

2. Materials and methods 2.1. SMBR The plexiglass SMBR (Fig. 1) had a working volume of 7.0 L. The hollow polypropylene bre membrane module employed in this study was 0.5 m long and had a pore size of 0:1 mm and surface area of 2:0 m2 . The process was maintained at 2025  C. The height was from liquid surface in the bioreactor to efuent port. The mixed liquor in the bioreactor was driven under the height by gravitation and passed through the hollow Activated sludge was taken from the aeration pool in Harbin Renery and was incubated in batch culture. After 7 days, MLSS reached 1858 mg L1 . An old membrane module (operated for 1 year in the same bioreactor) was added to the bioreactor to operate the SMBR continuously. Seven days later, MLSS reached 2820 mg L1 . The old membrane module was taken from the bioreactor and a new membrane module was added to the bioreactor to operate the SMBR. With incubation and acclimation for 14 days, the colour of the ocs changed to a brown colour. The amount of

Backwashing device

Thermometer Ballcock Hollow fibre membrane

Water balance tank

Sample port

Height Pump

Feed tank Air pump Gas flow meter

SMBR Air diffuser

Effluent
Fig. 1. Schematic diagram of the SMBR.

ARTICLE IN PRESS
N. Ren et al. / International Biodeterioration & Biodegradation 55 (2005) 279284 281

protozoa, such as rotifer species was observed through a microscope. Efuent COD was around 80 mg L1 . Based on the above, it was judged that the process of incubation and acclimation was completed. 2.4. SMBR operational conditions To maintain a stable HRT, an air-driven valve linked to an electromagnetic ow meter automatically controlled the ow rate of efuent. Dissolved oxygen was maintained at 2.03:0 mg L1 by adjustment of a rotary ow meter. Three membrane bioreactors operated synchronously in this study. The ux in the three bioreactors was 38.8, 58.3 and 116:7 ml min1 when the HRT was 3, 2 and 1 h, respectively. 2.5. Analytical methods Standard methods (APHA, 1995) were used to determine COD, MLSS, DO and pH values. The relation between MLSS and COD removal was analysed using the mathematical software program MATLAB, which from the literature does not appear to have been used previously for analysis of this relationship in the SMBRs.

viewed that the removal of organic pollutants was a cofunction of microbial metabolism and membrane ltration. The efuent COD concentration reached a level of o30 mg L1 , and even fell to 10 mg L1 , although the inuent COD uctuated from 350 to 500 mg L1 . When the HRT was 2 h, the COD removal uctuated between 88.5% and 97.3% and the efuent COD between 41.6 and 10:8 mg L1 . COD removal was therefore very high when the HRT was either 2 or 3 h, and the efuent COD was less than 30 mg L1 . This is sufcient to meet the reused water quality standard in China. When the HRT was 1 h, COD removal increased with the increase in MLSS. The COD removal uctuated from 80.0% to 91.1% and efuent COD from 63.4 to 35:8 mg L1 . This meets the water quality standard for discharge in China. It can therefore be concluded that the removal of organic pollutants was high and stable when SMBR technology was applied to treat domestic sewage.

3.2. Effect of MLSS on the COD removal at different HRTs The effect of MLSS on COD removal (Fig. 3) showed the same trend at different HRTs. The mathematical analysis of the relations between MLSS and COD removal was developed based on the experimental data to describe this trend using software of MATLAB. A fourth-order polynomial function (1) was considered to simulate the data in Fig. 3 y a4 x4 a3 x3 a2 x2 a1 x a0 . (1)

3. Results and discussion 3.1. Effect of HRT on COD removal The changes in COD removal and efuent COD values with time for each of the three HRT settings are illustrated in Fig. 2. When the HRT was 3 h, the highest COD removal was 97.2%, after 50 days operation. It is

Unknown coefcients of a0 , a1 , a2 , a3 and a4 needed to be calculated by the equation group (2), where a matrix with ten rows and ve columns showed the coefcients.
100

100 140 95 COD removal (%) 90 85 80 40 75 70 30 32 34 36 38 40 42 44 46 48 50 time (day)

COD removal(HRT3h) Effluent COD(HRT3h) COD removal(HRT2h) Effluent COD(HRT2h) COD removal(HRT1h) Effluent COD(HRT1h)

95 120 COD removal (%) 100 80 60 Effluent COD(mg L1) 90

85
HRT3h HRT2h HRT1h

80

20 0 52 75

70 500

2500

4500

6500 L-1)

8500

10500

MLSS (mg

Fig. 2. COD removal at different HRTs.

Fig. 3. Effect of MLSS on COD removal at different HRTs.

ARTICLE IN PRESS
282 N. Ren et al. / International Biodeterioration & Biodegradation 55 (2005) 279284

1 x1 6 y 7 61 x 6 27 6 2 7 6 6 6 y3 7 6 1 x 3 7 6 6 7 6 6 6 y4 7 6 1 x 4 7 6 6 6 y5 7 6 1 x 5 7 6 6 76 6 6 y6 7 6 1 x 6 7 6 6 6 y7 7 6 1 x 7 7 6 6 7 6 6 6 y8 7 6 1 x 8 7 6 6 6 y 7 6 1 x9 4 95 4 y10 1 x10

y1

x2 1 x2 2 x2 3 x2 4 x2 5 x2 6 x2 7 x2 8 x2 9 x2 10

x3 1 x3 2 x3 3 x3 4 x3 5 x3 6 x3 7 x3 8 x3 9 x3 10

3 x4 1 x4 7 2 7 7 x4 7 2 3 3 7 a0 7 x4 7 6 7 4 7 6 a1 7 x4 7 6 7 5 7 76 a2 7. x4 7 6 7 6 7 6 7 4 a3 5 x4 7 7 7 a4 7 x4 7 8 7 x4 7 9 5 x4 10

(2)

MATLAB would output a row vector of the polynomial (Gander, 1999; Ren et al., 2001; Su, 2002). The calculation of coefcients showed as follows: When the HRT was 1 h, a0 74:000, a1 0:0035, a2 3:7e 007, a3 1:1e 010 and a4 5:9e 015; when the HRT was 2 h, a0 77:000, a1 0:0023, a2 3:3e 006, a3 6:2e 010 and a4 3:4e 014; and when the HRT was 3 h, a0 85:000, a1 0:0082, a2 7:6e 006, a3 1:7e 009 and a4 1:1e 013. Consequently, the following three mathematical models could be obtained with regard to the effect of MLSS on COD removal at different HRT: y1 5:9e 015x4 1:1e 010x3 3:7e 007x2 0:0035x 74:000, y2 3:4e 014x4 6:2e 010x3 3:3e 006x2 0:0023x 77:000, y3 1:1e 013x4 1:7e 009x3 7:6e 006x2 0:0082x 85:000. The comparison of simulated results and the original data (Fig. 4) demonstrated that the fourth-order polynomial was very stable. In order to analyse the relation of COD removal and MLSS more directly, Z and M respectively replaced y and x, and the following mathematical model was obtained. Z k4 M 4 k3 M 3 k2 M 2 k1 M DZ. (3)

Here Z is COD removal, M is MLSS, k1 , k2 , k3 , k4 are constants, and DZ is a constant item, which is dened by COD removal when M is equal to zero. Table 1 shows the mathematical model and correlative mathematical parameters of the effect of MLSS on COD removal at different HRTs in this experiment, from which it is concluded that: (i) Fig. 4 and Eq. (3) show that Z increased with the increase of M. When M increased to 6000 mg L1 , the trend of Z gradually became stable. At the start, the membrane bioreactor MLSS was very low, and consequently, the microbial metabolism and COD removal were quite low. After that, the sludge continued to increase and COD removal also increased. However, when the MLSS arrived at a particular value MLSS 6000 mg L1 COD removal and efuent COD were stable, as a result of a stable gelatin layer at the surface of the membrane. Therefore, the simulation results for this mathematical model showed that the optimum MLSS should be maintained at around 6000 mg L1 in the SMBR. (ii) Because of k4 5k3 5k2 , the fourth degree equation could be replaced by the second degree equation Z k2 M 2 k1 M DZ. (4)

(iii) Supposing N s stands for sludge removal loading rate, S 0 for inuent COD, S e for efuent COD and t stands for hydraulic retention time. According to the equation for active sludge kinetics, N S S 0 S e =M t, it can be deduced that M S0 Se . NS t (5)

Accordingly, the mathematical model for COD removal with the change of sludge loading rate: Z k2 S0 Se 2 S0 Se DZ. k1 2 2 NS t NS t (6)

Formula (6) shows that COD removal Z was related to HRT t, the COD of inuent S 0 and sludge loading rate N s . Perfect COD removal could be gained by adjusting parameters such as t, S 0 and N s . In addition, the coefcients of simulation and norm of residuals at different HRTs were used to validate the

Fig. 4. Curve simulation results at HRT of (a) 1 h (b), 2 h and (c) 3 h.

ARTICLE IN PRESS
N. Ren et al. / International Biodeterioration & Biodegradation 55 (2005) 279284 Table 1 Correlative mathematical parameters and models of COD and MLSS removal at different HRTs HRT (h) 1 2 3 DZ 74 77 85 Mathematical model y1 5:9e 015x4 1:1e 010x3 3:7e 007x2 0:0035x 74:000 y2 3:4e 014x4 6:2e 010x3 3:3e 006x2 0:0023x 77:000 y3 1:1e 013x4 1:7e 009x3 7:6e 006x2 0:0082x 85:000 k=k1 , k2 , k3 , k4 0:0035 3:7e 007 1:1e 010 5:9e 015 0:0023 3:3e 006 6:2e 010 3:4e 014 0:0082 7:6e 006 1:7e 009 1:1e 013 283

removal gradually stabilised. It was demonstrated that the optimum MLSS in an SMBR should be maintained at around 6000 mg L1 . (3) Formula, Z k2 S0 Se 2 S0 Se DZ, k1 2 2 NS t NS t

showed that COD removal Z was related to HRT t, inuent COD S 0 and sludge removal loading rate N s . Perfect removal of COD could be obtained by adjusting these three parameters.

Acknowledgements The present publication has been made possible through the nancial, technical and administrative assistance of China National 863 Hi-Tech R & D Program.

References
APHA,1995. Standard Methods for the Examination of Water and Wastewater, 20th ed. American Public Health Association, Washington, DC. Brindle, K., Stephenson, T., 1996. Application of membrane biological reactors for the treatment of wastewaters. Biotechnology and Bioengineering 49, 601610. Chiemchaisri, C., Yamamoto, K., Vigneswaran, S., 1993. Household membrane bioreactor in domestic wastewater treatment. Water Science and Technology 27, 171178. Defrance, L., Jaffrin, M.Y., 1999. Comparison between ltrations at xed transmembrane pressure and xed permeate ux: application to a membrane bioreactor used for wastewater treatment. Journal of Membrane Science 152, 203210. Devies, W.J., Le, M.S., Heath, C.R., 1998. Intensied activated sludge process with submerged membrane microltration. Water Science and Technology 38, 421428. Gander, W., 1999. Solving Problems in Scientic Computing Using Maple and MATLAB. China Higher Education Press Beijing/ Springer, Berlin. Gu, G.W., He, Y.L., 2002. Study and Application of the Membrane Bioreactor in Wastewater Treatment. China Chemistry Industry Press, Beijing. Guender, B., Krauth, Kh., 1998. Replacement of secondary clarication by membrane separation: results with plate and hollow bre modules. Water Science and Technology 38, 383393. Halil, H., Cumali, K., Ayhan, U., 2002. Viability of microbial mass in a submerged membrane bioreactor. Desalination 150, 263268.

Fig. 5. Residuals of curve simulation at HRT of (a) 1 h (b), 2 h and (c) 3 h.

correctness of our mathematical models. Fig. 5 indicates that when the HRT was 3, 2 or 1 h all the norms of residuals were o3:0 (Wen et al., 2000; Su, 2002), proving that the model could simulate the experimental data correctly.

4. Conclusions (1) When the SMBR was used to treat domestic sewage, the experimental results showed that an HRT of 1 h could meet the normal standard for discharged domestic sewage, and an HRT of 2 h could meet that for water reclamation. (2) Mathematical analysis of the experimental data showed that COD removal increased with increase of MLSS. When MLSS increased to 6000 mg L1 , COD

ARTICLE IN PRESS
284 N. Ren et al. / International Biodeterioration & Biodegradation 55 (2005) 279284 Stefan, H., Walter, T., 2001. Treatment of urban wastewater in a membrane bioreactor at high organic loading rates. Journal of Biotechnology 92, 95101. Su, X.S., 2002. Engineering Application of MATLAB 6.0. China Science Press, Beijing. Trouve, E., Urbain, V., Manem, J., 1994. Treatment of municipal wastewater by a membrane bioreactor: results of a semi-industrial pilot-scale study. Water Science and Technology 30, 151157. Ueda, T., Hata, K., Kikuoka, Y., 1996. Treatment of domestic sewage from rural settlements by a membrane bioreactor. Water Science and Technology 34, 189196. Urbain, V., Mobarry, B., Silva, V., Stahl, D.A., Rittmann, B.E., Manem, J., 1998. Integration of performance, molecular biology and modeling to describe the activated sludge process. Water Science and Technology 37, 223229. Wen, X., Zhou, L., Wang, D.L., Xiong, X.Y., 2000. Application Design of MATLAB NN. China Science Press, Beijing. Xing, C.H. Qian, Y., Wen, X.H., Meng, Y.B., 1998. Performance of microltration membrane bioreactor for domestic wastewater reclamation. In: Proceedings of WEFTEC Asia 98, January 1998, Singapore. Huang, X., Gui, P., Qian, Y., 2000. Performance of submerged membrane bioreactor for domestic wastewater treatment. Tsinghua Science and Technology 5, 237240. Knoblock, M.D., Sutton, P.M., Mishra, P.N., Gupta, K., Janson, A., 1994. Membrane biological reactor system for treatment of oily wastewaters. Water Environment Research 66, 133139. Makoto, O., Yutaka, O., Naoki, O., 1998. Decoloration system using rotation membrane UF module. Water Science and Technology 38, 3543. Ren, N.Q., Zhang, Y., Chen, Z.B., 2001. The mathematical model analysis of membrane ux by using submerged bioreactor with different membrane forms. High Technology Letters 11, 100103. Rosenberger, S., Kruger, U., Witzig, R., Manz, W., Szewzyk, U., Kraume, M., 2002. Performance of a bioreactor with submerged membranes for aerobic treatment of municipal wastewater. Water Research 36, 413420. Shim, J.K., Yoo, I.K., Lee, Y.M., 2002. Design and operation considerations for wastewater treatment using a at submerged membrane bioreactor. Process Biochemistry 38, 279285.